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Accuracy of a Recent Regularized Nuclear Potential

[Image: see text] F. Gygi recently suggested an analytic, norm-conserving, regularized nuclear potential to enable all-electron plane-wave calculations [Gygi J. Chem. Theory Comput.2023, 19, 1300–1309.]36757291. This potential V(r) is determined by inverting the Schrödinger equation for the wave fun...

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Autor principal: Lehtola, Susi
Formato: Online Artículo Texto
Lenguaje:English
Publicado: American Chemical Society 2023
Acceso en línea:https://www.ncbi.nlm.nih.gov/pmc/articles/PMC10339670/
https://www.ncbi.nlm.nih.gov/pubmed/37354116
http://dx.doi.org/10.1021/acs.jctc.3c00530
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author Lehtola, Susi
author_facet Lehtola, Susi
author_sort Lehtola, Susi
collection PubMed
description [Image: see text] F. Gygi recently suggested an analytic, norm-conserving, regularized nuclear potential to enable all-electron plane-wave calculations [Gygi J. Chem. Theory Comput.2023, 19, 1300–1309.]36757291. This potential V(r) is determined by inverting the Schrödinger equation for the wave function Ansatz ϕ(r) = exp[−h(r)]/√π with h(r) = r erf(ar) + b exp(−a(2)r(2)), where a and b are parameters. Gygi fixes b by demanding ϕ to be normalized, with the value b(a) depending on the strength of the regularization controlled by a. We begin this work by re-examining the determination of b(a) and find that the original 10-decimal tabulations of Gygi are only correct to 5 decimals, leading to normalization errors in the order of 10(–10). In contrast, we show that a simple 100-point radial quadrature scheme not only ensures at least 10 correct decimals of b but also leads to machine-precision level satisfaction of the normalization condition. Moreover, we extend Gygi’s plane-wave study by examining the accuracy of V(r) with high-precision finite element calculations with Hartree–Fock and LDA, GGA, and meta-GGA functionals on first- to fifth-period atoms. We find that although the convergence of the total energy appears slow in the regularization parameter a, orbital energies and shapes are indeed reproduced accurately by the regularized potential even with relatively small values of a, as compared to results obtained with a point nucleus. The accuracy of the potential is furthermore studied with s-d excitation energies of Sc–Cu as well as ionization potentials of He–Kr, which are found to converge to sub-meV precision with a = 4. The findings of this work are in full support of Gygi’s contribution, indicating that all-electron plane-wave calculations can be accurately performed with the regularized nuclear potential.
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spelling pubmed-103396702023-07-14 Accuracy of a Recent Regularized Nuclear Potential Lehtola, Susi J Chem Theory Comput [Image: see text] F. Gygi recently suggested an analytic, norm-conserving, regularized nuclear potential to enable all-electron plane-wave calculations [Gygi J. Chem. Theory Comput.2023, 19, 1300–1309.]36757291. This potential V(r) is determined by inverting the Schrödinger equation for the wave function Ansatz ϕ(r) = exp[−h(r)]/√π with h(r) = r erf(ar) + b exp(−a(2)r(2)), where a and b are parameters. Gygi fixes b by demanding ϕ to be normalized, with the value b(a) depending on the strength of the regularization controlled by a. We begin this work by re-examining the determination of b(a) and find that the original 10-decimal tabulations of Gygi are only correct to 5 decimals, leading to normalization errors in the order of 10(–10). In contrast, we show that a simple 100-point radial quadrature scheme not only ensures at least 10 correct decimals of b but also leads to machine-precision level satisfaction of the normalization condition. Moreover, we extend Gygi’s plane-wave study by examining the accuracy of V(r) with high-precision finite element calculations with Hartree–Fock and LDA, GGA, and meta-GGA functionals on first- to fifth-period atoms. We find that although the convergence of the total energy appears slow in the regularization parameter a, orbital energies and shapes are indeed reproduced accurately by the regularized potential even with relatively small values of a, as compared to results obtained with a point nucleus. The accuracy of the potential is furthermore studied with s-d excitation energies of Sc–Cu as well as ionization potentials of He–Kr, which are found to converge to sub-meV precision with a = 4. The findings of this work are in full support of Gygi’s contribution, indicating that all-electron plane-wave calculations can be accurately performed with the regularized nuclear potential. American Chemical Society 2023-06-24 /pmc/articles/PMC10339670/ /pubmed/37354116 http://dx.doi.org/10.1021/acs.jctc.3c00530 Text en © 2023 The Author. Published by American Chemical Society https://creativecommons.org/licenses/by/4.0/Permits the broadest form of re-use including for commercial purposes, provided that author attribution and integrity are maintained (https://creativecommons.org/licenses/by/4.0/).
spellingShingle Lehtola, Susi
Accuracy of a Recent Regularized Nuclear Potential
title Accuracy of a Recent Regularized Nuclear Potential
title_full Accuracy of a Recent Regularized Nuclear Potential
title_fullStr Accuracy of a Recent Regularized Nuclear Potential
title_full_unstemmed Accuracy of a Recent Regularized Nuclear Potential
title_short Accuracy of a Recent Regularized Nuclear Potential
title_sort accuracy of a recent regularized nuclear potential
url https://www.ncbi.nlm.nih.gov/pmc/articles/PMC10339670/
https://www.ncbi.nlm.nih.gov/pubmed/37354116
http://dx.doi.org/10.1021/acs.jctc.3c00530
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